This study utilized the Community Multiscale Air Quality (CMAQ) model to assess the impact of open biomass burning (OBB) in Thailand and neighboring countries—Myanmar, Laos, Cambodia, and Vietnam—on the PM2.5 concentrations in the Bangkok Metropolitan Region (BMR) and Upper Northern Region of Thailand. The Upper Northern Region was further divided into the west, central, and east sub-regions (WUN, CUN, and EUN) based on geographical borders. The CMAQ model was used to simulate the spatiotemporal variations in PM2.5 over a wide domain in Asia in 2019. The Integrated Source Apportionment Method (ISAM) was utilized to quantify the contributions from OBB from each country. The results showed that OBB had a minor impact on PM2.5 in the BMR, but transboundary transport from Myanmar contributed to an increase in PM2.5 levels during the peak burning period from March to April. In contrast, OBB substantially impacted PM2.5 in the Upper Northern Region, with Myanmar being the major contributor in WUN and CUN and domestic burning being the major contributor to EUN during the peak months. Despite Laos having the highest OBB emissions, meteorological conditions caused the spread of PM2.5 eastward rather than into Thailand. These findings highlight the critical impact of regional transboundary transport and emphasize the necessity for collaborative strategies for mitigating PM2.5 pollution across Southeast Asia.